Thienyl ethylene compounds



' to form useful oils and resins.

Patented Oct. 17, 1950 UNITED STATES PATENT ornce THIENYL ETHYLENE COMPOUNDS Isaac C. Beatty, III, Williamstown, Mass, as-

signor to Sprague Electric Company, North Adams, Mass, a corporation of Massachusetts No Drawing. Application July 27, 1946,

Serial No. 686,730

6 Claims. 1

wherein R represents a monovalent organic radical, preferably a hydrocarbon group which may, if desired, be further substituted. In a still more restricted sense, this invention is concerned with thienyl compounds conforming to the general formula:

Ut S (5H2 wherein R represents a monovalent aryl radical, preferably of the benzene series.

The invention is also specifically concerned with the hydrogenated derivativesof the foregoing compounds or their polymers.v Thethiophene ring, the ethylene side chain or both may 1- (p-diphenyl) -1- (2'-thienyl) -ethylene 1-xyly1-1-(2-thienyl) -ethylene l-acenaphthenyl-l- (2-thienyl) -ethy1ene l-plienanthryl-l- (2 -thienyl) -ethylene l-fluoryl-l- (2-thienyl) -ethylene l-anthryl-l 2 -thienyl) -ethylene l-(m trifiuoromethylphenyl) 1 (2-thienyl)- ethylene 1-( p-chlorophenyl) -1- (2'-thienyl) -ethylene 1- (p-fluorophenyl) -l- (2 -thienyl) -ethylene 1- (o-nitrophenyl) -1- (2' -thieny1) -ethylene l-(o-aminoph'enyl) -1-(2'-thienyl) -ethylene l- (p-methoxy phenyl) -l- (2'-thienyl) -ethylene 1,1-bis(2-thienyl) -ethylene' l- (2' -thienyl) -l- (2'-pyrryl) -ethylene l-p(2'-thienyl) -1- (2-pyridyl) -ethylene 1- (2 thienyl) -l- (2 -indyl) -ethylene 1- (2'-thieny1) 1-(2-fury1) -ethy1ene binol.

1- (Zrthienyl) -l (2-piperidyl) -ethylene -1- (2 -thienyl) -1- (3f-gcarbazyl) -ethy lene as well as the polymers of the above compounds and the corresponding ethane compounds produced by hydrogenation of the ethylene double bond.

The compounds of this invention are readily prepared by reacting acetothienone with the appropriate Grignard intermediate. The tertiary carbinol thus formed dehydrates very readily, spontaneously in some cases, to form the ethylene compounds. The latter may be polymerized by conventional means to form dimers, trimers, and higher polymers, which are oils or resinous solids.

The following examples illustrate the manner of producing the compounds of this invention.

EXAMPLE 1 I Preparation of 1-phnyZ-1-(2-thienyl) ethylene One mole of bromobenzene was added to 1.05 moles of magnesium in 700 ml. of dry ether, and the mixture was refluxed for one hour to complete the reaction. At the end of this time 1 mole of acetothienone was added with continuous agitation. The heat of reaction caused. continued reflux for some time, after which heat was applied and the material refluxed and agitated for four hours to complete the reaction.

The mixture was then poured onto a mixture of 1000 gms. of ice and 250 cc. of 00110. hydrochloric acid. The mix Was extracted with ether,

washed with dilute sodium carbonate and water, 7

dried over calcium chloride and the ether 'was distilled off.

A small amount of potassium acid sulfate was added and the residue (from ether distillation) was heated up to C. at atmospheric pressure to remove all of the water split off from the car- The solution was cooled, extracted with 7 I ether, washed with sodium carbonate and water and dried over calcium chloride, after which the ether was distilled off. The residual product was then distilled at 106 C./2 mm. to give a liquid monomer of N 1.5890. The residue which did not boil at 140 C 3 mm. was an amber resin with a softening point of about 45 C.-55 C., and is believed to be a low polymer of the l-phenyl-l-(2-thienyl)-ethylene referred to above as a liquid. 'The resin had a refractive index of N 1.3678.

EXAlVIPLE 2 Preparation of 1 (p-tolyl) -1 (2-thienyl) ethylene Para-bromotoluene was substituted for the bromobenzene of Example 1, the procedure being otherwise the same. The monomeric liquid product boiled at 86-88 (1/35 microns. Some yield of a low polymer, probably a dimer or trimer, was obtained. This boiled at 180-205 (1/38 microns.

EXAMPLE 3 Preparation of 1 (m-tolyl) -1- (2'-thz'enyl) ethylene Meta-bromo toluene was substituted for the bromobenzene of Example 1, the procedure being otherwise the same. The m-tolyl product was a liquid, B. P. l02-105 (3140-60 microns.

EXANIPLE 4 Preparation of 1- (m-trz'fluoromethylphenyl) 1 (2' -thienyl) -ethylene Meta bromobenzotrifluoride was substituted for the bromobenzene of Example 1, the procedure being otherwise the same. A high yield of the liquid product was obtained, B. P. 90-l05 C./.1.2 mm. The liquid froze to a solid state at about 16 C.

EXAMPLE 5 Preparation of Z-(aZpha-naphthyl) -1- (2'-th,ienyl) -ethylene invention. These are produced by hydrogenating the thiophene ring, either during or following the hydrogenation of the ethylene double bond.

The compounds of the invention are useful as dielectric oils and resins, as pharmaceutical intermediates, dyestuff intermediates and the like. The dimers and trimers may be used as substitutes for the mineral oils conventionally employed in electrical capacitors, due to their relatively high boiling points and dipole moments. The higher polymers-either homopolymers or copolymers, produced by conventional polymerization methods with styrene, vinyl carbazole and other polymerizable compoundsmay be used for many purposes wherein resins have previously been employed.

As many widely different embodiments of this invention may be made without departing from the spirit and scope hereof, it is to be understood that the invention is not limited to the specific embodiments hereof except as defined in the appended claims.

What I claim is:

l. A compound conforming to the formula wherein R represents a monovalent aryl radical. 2. A compound conforming to the formula wherein R. represents a monovalent phenyl radical.

3. l-phenyl-l- (2'-thienyl) -ethylene.

4. l-(p-tolyl)-1-(2'-thienyl) -ethylene.

5. 1-(m-trifiuoromethylphenyl) l (2'-thienyl) -ethylene.

6. A compound conforming to the general formula wherein R represents a monovalent cyclic organic radical selected from the group consisting of aryl, pyrryl, pyridyl, indyl, furyl, quinolyl, piperidyl and carbazyl radicals.

ISAAC C. BEATTY, III.

Chemical Abstracts, 27:2443 (5) 25:4238 (8) (1931).

. Richter: Organic Chemistry, pp. 649, 650, John Wiley, 1938. 

6. A COMPOUND CONFORMING TO THE GENERAL FORMULA 